NOTE

P H Y S I C S

KINETIC THEORY
GAS LAWS

What you already know What you will learn

• Thermal expansion • States of matter

• Thermal stress • Characteristics of gas
• Specific heat • Macroscopic properties of gases
• Latent heat • Gas laws
• Joule’s law • Ideal gas equation
• Principle of calorimetry

States of Matter

The homogeneous phases in which matter can exist are known as states of matter. There are three
physical states of matter. They are as follows:

Matter

Solid Liquid Gas

1. Solids 2. Liquids 3. Gases

Solids have a Unlike solids, these In gases, the atoms
definite shape, size, substances have are very loosely
and volume. The a weaker bond packed due to
molecules in solids and generally do less intermolecular
are bonded strongly not have a definite forces, The gas
and the only possible shape. Liquids take molecules can
atomic motion is the shape of the fly apart in all
vibrational motion. container in which directions.
they are placed.

Characteristics of Gas

1. The gas has no shape and size. It can expand indefinitely and uniformly to fill the available
space.

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Volume of the gas = Volume available to the gas = Volume of the container

2. It exerts pressure on the walls of a

container in which it is kept because of
the collision of the gas molecules with
the walls of the container.

3. Intermolecular space:

Solid Liquid Gas

Gases have the highest intermolecular space between their molecules.

4. Density:

Solid Liquid Gas

Gases have the lowest density as there are less number of molecules per unit volume in the
gas.
5. Kinetic energy:
Gases have the highest kinetic energy as their molecules are continuously moving around.

Macroscopic Properties of Gases

Pressure

The gas molecules are constantly moving, causing constant collision with the walls of the container.
Due to these collisions, momentum of the gas molecules will change in a particular time interval
and hence the forces are applied on the walls. The normal force per unit area is the pressure
applied by the gas on the walls.

Volume

It is the freedom of the atoms to spread throughout the container.

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 03

Let us take a container filled with some gas and the piston is fixed on the top
of the container. On the movement of the piston slightly towards the outside
direction, the gas takes up the free space created on the top.
Volume of the gas = Volume available to the gas = Volume of the container

Temperature

With an increase in temperature, the speed of the gas molecule increases.

Ideal Gas

Assumptions of an ideal gas

The following are the assumptions made to consider a gas as ideal:

• The gas consists of a large number of molecules that are in random motion.
• The volume of the molecules is negligibly small compared to the volume occupied by the
gas.
• There are no (or entirely negligible) intermolecular forces between the gas molecules.
• All collisions between the molecules themselves, and between the molecules and the walls
of the container, are perfectly elastic.

NEET
Gas Laws

Boyle’s law

For a given mass of an ideal gas at a constant temperature, the volume of the gas is inversely
proportional to its pressure. P1
At constant temperature , P2
Pressure increased,
1
V∝ Volume decreased
P
k
⇒V =
P
⇒ PV =
k Pressure decreased,
V1 V2
Where, kk isis aconstant.
Where, constant. Volume increased
P
• Pressure vs volume graph:
As the product of pressure and volume of a given mass of gas is
always constant, the graph between them is a hyperbola as shown
in the figure. V
O

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 04

Some important graphs

1 1
1. P vs 2. V vs 3. PV vs P 4. PV vs V
V P

P V PV PV

1 1
O O O P O V
V P

Charles’s law

For a constant pressure, the volume of the given mass of a gas is directly proportional to its absolute
temperature.
At constant pressure,

V ∝T

⇒V =
kT

V
⇒ k
=
T
Where, k is a constant.
Let us assume that when a gas with initial volume V1 at temperature T1 is heated to a temperature
T2, the volume becomes V2 at a constant pressure.
Therefore,
V1 V2
=
T1 T2

Volume vs temperature graph for different scales:

V

1. Kelvin scale:
At absolute zero temperature, the volume
of gas is assumed to be zero.
O T (K)
V

2. Centigrade scale:
Since 0 °C = 273.15 K, the volume of the gas
becomes zero at –273.15 °C.

–273.15 K O T (°C)

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• At absolute zero temperature, Vgas = 0

• Straight line plots can be extrapolated to V = 0 (Practically impossible)
• Kelvin developed an absolute temperature scale by considering –273.15 °C as the lowest
approachable limit.

Some important graphs

1 1 V V
1. vs T 2. V vs 3. vs T 4. vs V
V T T T
1 V V
V
V T T

1
O T O O T O V
T

Gay-Lussac’s law

For a constant volume, the pressure of the Pressure vs temperature graph:

given mass of a gas is directly proportional to
its absolute temperature. P

At constant volume,
P ∝T
T
O
⇒P=
kT
P
⇒ k
=
T
Where, kk is
Where is constant.
a constant.

Some important graphs

P P 1 1
1. vs T 2. vs P 3. vs T 4. P vs
T T P T
P P 1
P
T T P

1
O T O P O T O T

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Avogadro’s law

For the same condition of temperature and pressure, equal volumes of different gases contain
equal numbers of molecules.
At constant pressure and temperature,

Volume of the gas (V ) ∝ Number of molecules in the gas ( n )

⇒V =
kn

Where, k is a constant.

Therefore, V

V1 V2
=
n1 n2

Where V1 , n1 are the initial volume and number of molecules, and

O n
V2 , n2 are the final volume and number of molecules, respectively.

Gas Laws

Boyle’s law Charles’s law Gay-Lussac’s law Avogadro’s law

n and T constant n and P constant n and V constant T and P constant

1
P∝ V∝T P∝T V∝n
V

Ideal Gas Equation

Ideal gas equation relates the pressure (P), volume (V) and temperature (T) of the given state of an
ideal gas.
By combining all four gas laws, we get,
PV ∝ nT
⇒ PV = nRT
Where , R Universal
= gas constant, and, n Number of moles .
PV
Thus, the universal gas constant, R =
nT
Note: 1 mole gas = 6.023 × 1023 number of gas molecules

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Value of universal gas constant (R)

At standard temperature pressure (STP) conditions,

P = 1 atm = 101325 Nm–2
n = 1 mole
V = 22.4 L = 22.4 × 10–3 m3
T = 273 K
We have ,
PV
R=
nT
Substituting all the values, we get the following:

101325 Nm−2 × 22.4 × 10−3 m3

R = 8= .314 Nm mol −1 K −1 8.314 J mol −1 K −1
1 mol × 273 K

Also, 1 cal = 4.18 J

1
cal
=R 8
=.314 × 4.18 1.98 cal mol −1 K −1 ≅ 2 cal mol −1 K −1
mol K

A gas occupies a volume of 400 cm3 at 27 ℃ and 780 mm of Hg. What volume (in litres) will it
occupy at 87 ℃ and 780 mm of Hg

(A) 0.48 (B) 480 (C) 0.24 (D) 240

Solution

Initially, we have,
Volume of the gas, V1 = 400 cm3
Pressure of the gas, P1 = 780 mm of Hg
Temperature of the gas, T1 = 27 °C = 27 + 273 = 300 K
Final pressure of the gas, P2 = 780 mm of Hg
Final temperature of the gas, T2 = 87 °C = 87 + 273 = 360 K
Here, the pressure is constant and only the temperature has changed.
By using Charles’s law,
V1 V2
=
T1 T2

By substituting the values of given volume and temperature at two conditions,we get the following:

400 V2
⇒ =
300 All rights
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 08

V1 V2
=
T1 T2

By substituting the values of given volume and temperature at two conditions,we get the following:

400 V2
⇒ =
300 360
400 × 360
⇒
= V2 cm3 0.48 L
= 480=
300
Thus, option (A) is the correct answer.

V P2
In the given (V-T) diagram, what is the relation between P1
pressures P1 and P2?

O T

(A) P2 = P1 (B) P2 > P1 (C) P2 < P1 (D) Cannot be predicted

NEET

Solution

From the ideal gas equation,

PV = nRT
PV
⇒ = nR
T
For a fixed amount of gas, nR is constant.
V C
⇒ = ( C is a constant )
T P
V 1
⇒ ∝
T P
For a graph of x - y,
y
= tan θ (Slope of the graph)
x
Similarly, for a V − T graph ,
V  1
⇒  = tan θ  ∝
T  P
If θ increases, then tan θ will increase.
V P2
We know, θ2 > θ1
P1
⇒ tan θ2 > tan θ1 θ2
As tan θ is inversly proportional to P , P2 < P1 . θ1
Thus, option (C) is the correct answer. O T

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 NOTE
P H Y S I C S

KINETIC THEORY
GAS EQUATION

What you already know What you will learn

• States of matter • Dalton's law of partial pressure

• Gas and its characteristics • Diffusion and effusion
• Macroscopic properties of gases • Graham's law of diffusion
• Assumptions of an ideal gas and its • Ideal gas equation
equation • Real gases
• Gas laws • Van der Waals equation for gases

Dalton’s Law of Partial Pressure

At constant temperature, the total pressure exerted by a mixture of

two or more non-reacting gases in a definite volume is equal to the
sum of the partial pressures exerted by each individual gas in the
mixture.
Let us assume a container filled with n number of non-reactive gases,
and the pressure of the container is kept constant. So, the total
pressure exerted by the gases (PT) is given as follows:
PT = P1 + P2 + P3 + …… + Pn
Where, P1, P2, P3, …… , Pn represents the partial pressures of n individual
gases.
The partial pressure of a gas is always directly proportional to the number of moles of the gas. It
means that a gas with a higher number of moles will exhibit a higher partial pressure.
A system containing a mixture of n non-reacting gases can be visualised as a superposition of
the individual gases at their respective partial pressures and the temperature equal to that of the
system.

P1 P2 P3

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For each gas, we can apply the ideal gas equation, considering that the volume occupied by the
individual gases will be the same as that of the volume of the container (V).
The partial pressure of the first gas, P1V = n1RT
The partial pressure of the second gas, P2V = n2RT
The partial pressure of the nth gas, PnV = nnRT

For a mixture of two gases inside a container

Let the total pressure of a mixture be PT , and the partial pressures of the individual gases be P1 and
P2 , and the numbers of the moles of the gases be n1 and n2 respectively.
For the mixture, we can write the ideal gas equation as follows:
PT=
V ( n1 + n2 ) RT
Where,
V is the volume of the container.
R is the universal gas constant.
Since the individual gases are occupying the whole container, we can write the ideal gas equation
for them as follows:
The partial pressure of the first gas, P1V = n1RT
The partial pressure of the second gas, P2V = n2RT
On comparing the given equations, we get,
PT V n1RT + n2 RT
=

⇒ PT V = P1V + P2V

⇒ PT = P1 + P2
This is the expression for Dalton's law for a mixture of two non-reacting gases.

Three containers of same volume contain three different gases. The masses of the molecules
are m1, m2, and m3, and the numbers of the molecules in the respective containers are N1, N2,
and N3. The gas pressures in the containers are P1 ,P2, and P3 respectively. All the gases are now
mixed and put in one of the containers. What will be the pressure (P) of the mixture?

P + P2 + P3P1 + P2 + P3P1 + P2 + P3P1 + P2 + P3

(A) P < P1 + P2 P+<P3P1 +PP=2P+<1P3(B)
P1 +PP2=P+<P3P1 P+P=P2=P+ P3P2P+P=P=P
1 + +PP>P+P=PP+1 P+PP+2P
(C) =PP3+ P+ P+>P
>P+P +PP1 (D)
+ P2P+>PP31 + P2 + P3
3 3 3 3 1 23 1 3 2 3 1 1 2 2 3 3

Solution

When all three gases are mixed, the net Hence P1, P2, and P3 represent the respective
pressure of the mixture will be the sum of the partial pressures of the gases.
partial pressures of each gas. Volume of the gas mixture = Volume of the
The pressure of each container indicates the container = V
partial pressure of an individual gas because From Dalton’s law of partial pressure,
the numbers of the moles of gases will remain PT = P1 + P2 + P3
fixed even after mixing them together. ⇒ P = P1 + P2 + P3
Thus, option (C) is the correct answer.

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Diffusion

Diffusion is defined as the spontaneous intermixing of gas molecules under a concentration

gradient.
• Whenever a fluid is allowed to move freely, it will tend to diffuse by moving from a region of
higher concentration to a region of lower concentration. The difference in the concentrations
is known as the concentration gradient.
• For example, if we put a drop of ink in a glass of water, the ink will immediately spread out to
the region of lower concentration (i.e., towards the clear water) such that the concentration
gradient in the liquid is minimised.
• The aroma of food being cooked at a farther distance is sensed by us due to the phenomenon
of diffusion of gas molecules.

Effusion

The escape of gas molecules from high pressure to low pressure/vacuum through a pinhole without
molecular collision is known as effusion. In this case, the size of the orifice through which the gas
molecules are escaping is very small.
• A classic example to visualise effusion is the reduction in size of a gas-filled balloon, wherein
the gas molecules have leaked out through tiny pores.
• A container filled with gas in two partitions will exhibit effusion if a very small orifice is made
in the partition. In this case, the gas molecules will effuse from the high-pressure region to
the low-pressure region.

Graham’s law of effusion

The rate of effusion of a gas is inversely proportional to the square root of the density of the gas.
It can be logically understood that the lighter gas molecules will have a higher tendency to escape
through an orifice when compared to that for the case of heavier gas molecules.
1
∴r∝
ρ
Where, r is the rate of effusion and ρ is the density of the gas molecule.
The density of a gas is directly proportional to its molar mass (M).
⇒ρ∝M
So, the expession for the rate of effusion changes as follows:
1
⇒r ∝
M
k
⇒r =
M
Where, k is the proportionality constant.

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Graham’s Law of Diffusion

When two gases at the same pressure and temperature are allowed to diffuse into each other, the
rate of diffusion of each gas is inversely proportional to the square root of the density of the gas.
If two gas containers are connected through a valve at the same pressure and the valve is opened,
then the gas molecules will start to diffuse.

1 2 1 2
Relation between the rates of diffusion of gases is,
k
r=
ρ
k k
Hence, r1
= = and r2
ρ1 ρ2
r1 ρ
⇒ =2
r2 ρ1
ρ ∝ M
r1 ρ2 M2
⇒ = =
r2 ρ1 M1
Here, r1 and r2 represent the rates of diffusion of the respective gas molecules, 𝜌1 and 𝜌2 are
densities of the respective gases, and M1 and M2 represent the molar masses of the respective
gases.

Ideal Gas Equation

For n moles of an ideal gas,

PV = nRT
Here, P is the pressure exerted on the gas, V is the volume occupied by the gas, R is the universal
gas constant and T is the temperature of the gas.

This equation is also known as the equation of state because it provides the relationship
between pressure, volume, and temperature of the gas, wherein P, V, and T are the
parameters required to represent the state of a gaseous system.

Ideal gas equation in terms of molecules of gas

We have,
NA molecules of gas = 1 mol of gas

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 05

1
1 molecule of gas = mol of gas
NA
Substituting the value of moles in the equation PV = nRT, we get the following:
1  R 
⇒ PV
= RT
=  =T kT
NA  NA 
R
Here, is the Boltzmann constant (k) and it is defined as the gas constant per mole.
NA
R 8.314
k
= = = 1.38 × 10−23 JK −1
N A 6.023 × 1023
For N molecules of gas,
PV = NkT

Ideal gas equation in terms of grams of gas

1 mol of an ideal gas = M gram

(Where, M = Molar mass of the ideal gas)
1
1 gram of gas = mol
M
Substituting the value of moles in the equation PV = nRT, we get the following:
1 R
PV
= = RT  =
T rT
M M
R
Here, is known as the specific gas constant (r) and it is defined as the gas constant per gram of
M
gas.
R
∴ r = J g −1K −1
M
For m gram molecules of gas,
PV = mrT

Ideal gas equation in terms of density

We have,
PV = nRT
Mass of the gas ( in gram ) m
Moles of the gas ( n ) =
Molar mass of the gas ( in gram ) M
m
⇒ PV =
 M  RT
 
m
⇒ PM =
 V  RT
 
⇒ PM =ρ RT
Where, ρ is the density of the ideal gas.

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 06

Real Gases

The gases which do not obey ideal gas law exactly under all
conditions of temperature and pressure are known as real CO CH4
PV H2
gases.
He
The graph of PV-P shown in the figure depicts the behaviour of
different real gases under varying conditions of temperature Ideal gas
and pressure.
In the given graph, we can see that methane (CH4) has the
maximum downward shift in the low pressure region due to P
O
its highest molecular weight among the given gases.

• For a particular gas, the curve will shift upwards with an increase in temperature.
• For a given set of gases at a fixed temperature, the curve will shift upwards with a
decrease in the molecular weight of the gas in a region of low pressure.
• For a given set of gases at a fixed temperature, the curve will shift downwards with the
increase in the molecular weight of the gas in a region of low pressure.

Deviation of real gases from ideal behaviour

• When the PV-P graph is a straight line that is parallel to the P-axis, then it represents ideal gas
behaviour.
• When the PV-P graph is showing an upward shift with respect to the ideal gas behaviour, then
it is known as a positive deviation.
• When the PV-P graph is showing a downward shift with respect to the ideal gas behaviour, then
it is known as a negative deviation.

Comparison of P-V graphs for a real gas and an ideal gas

• If we look at a fixed pressure for both real and ideal

gases by drawing a straight line parallel to the V-axis
in a high-pressure region, we get,
Vreal > Videal. P
This indicates that at a higher pressure, the dominance Ideal gas
of the repulsive forces leads to a higher volume in the Real gas
case of real gases.
• If we look at a fixed pressure for both real and ideal
gases by drawing a straight line parallel to the V-axis
in a low-pressure region, we get,
Vreal < Videal. O V
It indicates that at a lower pressure, the dominance
of the attractive forces leads to a lower volume in the
case of real gases.

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 07

Why do real gases deviate from ideal gas behaviour?

The enlisted points are the main reasons for the difference in behaviour exhibited by a real gas in
comparison with an ideal gas.
• In case of ideal gas, we assume negligible intermolecular interactions. However, in reality,
the gas molecules do interact with each other through weak attractive forces.
• In case of ideal gas, we neglect the volume occupied by the gas molecules. Thus, for an ideal
gas,
Volume occupied by the gas = Volume of the container
However, in reality, the gas molecules do occupy some volume. Thus, for a real gas,
Volume occupied by the gas ≠ Volume of the container
The volume available for a real gas will be less than V.

Real Gas vs Ideal Gas

• The volume of the real gas particles is not negligible with

respect to the container.
• Ideal gases cannot be liquified but real gases occupy a
finite volume on liquefaction.

Ideal gas Real gas

• Intermolecular forces of attraction operate between gas

molecules in real gases. However, in the case of an ideal
gas, we consider the intermolecular forces to be negligible.

Ideal gas Real gas

• In the case of an ideal gas, no energy is lost during the

collision of gas molecules, as the collision between
molecules is assumed to be elastic in nature.
However, in a real gas, the collision between molecules
and the walls of the container is inelastic in nature.
Inelastic collision
Real gas

NEET
Van der Waals Equation for Gases

For ideal gases,

PV = nRT
⇒ PidealVideal =
nRT

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 08

However, due to the presence of intermolecular forces and finite volume of gas molecules, the
given equation cannot be applied for real gases.
PrealVreal ≠ nRT
Thus, the ideal gas equation needs to be first modified in order to use them for real gases.
This modified version of the ideal gas equation was introduced by Van der Waals and it is therefore
known as the Van der Waals gas equation.
To obtain the Van der Waals gas equation, the following corrections have been done in the ideal
gas equation:
• Pressure correction
• Volume correction

Pressure correction

The gas molecule striking the wall of the container will be

attracted by the neighbouring gas molecules (through weak
intermolecular forces). This will lead to the reduction in speed
during the collision with the container.
Thus, the transfer of momentum will be reduced and
consequently, the applied force on the wall of the container
will reduce.
Hence, the pressure exerted by gas molecules will be less in Ideal gas Real gas
the case of real gases.
Pideal > Preal
⇒ Pideal =Preal + dP
Here, dP is the pressure-correction term.
an2
⇒ dP =2
V
Where, a = Van der Waals constant
And, a ∝ Attractive forces
an2
⇒ Pideal = Preal +
V2

Volume correction

For an ideal gas, the volume available for the free motion of the gas molecules is the entire volume
of the container because the volume of the gas molecules has been neglected.
Videal = Volume available for the free motion of gas = Vfree
However, for a real gas, some part of the volume of the container is occupied by the gas molecules.
Hence, less volume is available for the free motion of gas.
⇒ V free= Vcontainer − Vexcluded ⇒ V free= Vcontainer⇒−VVexcluded
= Vcontainer − Vexcluded
⇒ V free = Vcontainer − Vexcluded free
Vcontainer =of
V the container, Vcontainer = V
VVolume
container = V
Vcontainer = V
Vexcluded = occupied
nb Vexcluded = nb Vexcluded = nb
VVolume
excluded = nb
by the gas molecules,
⇒ V free = V − nb ⇒ V free = V − nb⇒ V free = V − nb
⇒ V free = V − nb

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 09

Where, b = Volume of one mole of gas particles

And, b ∝ Size of the gas molecule
Here, the excluded volume refers to the volume occupied by the molecules of a real gas, which is
not available for the free motion of the gas.
On substituting the terms of modified pressure and volume in the ideal gas equation, we get,
PidealVideal = nRT
 an2 
⇒  Preal + 2  (V − nb ) =
nRT
 V 
 an2 
This is the required Van der Waals gas equation. Here,  2  is the pressure-correction term and
(nb) is the volume-correction term. V 

• a = Attraction coefficient,
Which depends upon the strength of the intermolecular forces of attraction.
• b = Excluded volume per mole of the gas,
Which depends upon the size of the gas molecules.
• F or a gas with a high molar mass, the value of the attraction coefficient as well as that
of the excluded volume will increase.

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 NOTE
P H Y S I C S

KINETIC THEORY
PRESSURE AND SPEED

What you already know What you will learn

• Dalton's law of partial pressure • Compressibility factor

• Diffusion and effusion • Special cases of Van der Waals equation
• Graham's law of diffusion • Various speeds of gas molecules
• Ideal gas equation • Maxwell’s speed distribution curve
• Real gases • Mean free path
• Van der Waals equation for gases

Recap

In the last session, we understood the Van der Waals equation.

 an2 
 Preal + 2  (V − nb ) =
nRT
 V 
an2
In the equation , 2 is the pressure correction term and nb is the volume correction term.
V
Where, a and b are constants with very small values.

Compressibility Factor(Z)

The deviation from the ideal behaviour can be measured in terms of compressibility factor(Z).
Let us take a mole of an ideal gas. It will follow the ideal gas equation,
PV = nRT
For one mole of an ideal gas, n is equal to 1.
PV = RT
PV
=1
RT
So, the compressibility factor for the ideal gas is,
PV
Z
= = 1
RT
Compressibility factor can also be defined as the ratio of the observed volume of the gas to the
calculated volume at the same values of n, T, and P.

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 02

V real
Z =
V ideal
In general for a gas, the observed volume can be obtained from the experiment and the calculated
volume can be obtained by the ideal gas equation, i.e., Pideal Videal = nRT, for the same pressure and
temperature.

Different values of Z

Z=1 Z≠1

Vreal = Videal Vreal ≠ Videal

PV = nRT PV ≠ nRT
Ideal gas Real gas

For real gases, Z ≠ 1

Z≠1

Z>1 Z<1

Vreal > Videal Vreal < Videal

Repulsive forces Attractive forces
are dominating. are dominating.

The value of Z also determines whether we can liquefy a gas or not.

• For an ideal gas, liquefaction is not possible.
• For real gases, where Z > 1, it is difficult to liquefy; and if Z < 1, it is easy to liquefy.

For real gases, Z can be more than one, less than one, or in some cases it can be one.

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 03

Z=1 Z>1 Z<1

Vreal = Videal Vreal > Videal

Vreal < Videal
Fatt = Frep = 0 Frep > Fatt
Frep < Fatt
Liquefaction Difficult to
Easy to liquefy
not possible liquefy

Graph Between Compressibility Factor and Pressure

• Ideal gases
Z

Ideal gas
Z=1

O P

• Real gases
Z Real gas
C
Z>1
Ideal gas
A Z=1
B Z<1

O P

Low pressure zone High pressure zone

In region AB, the graph deviates below the ideal gas graph in the low-pressure zone. This deviation
from the graph of the ideal gas is known as negative deviation. For this region, Z < 1.
In region BC, the graph deviates above the ideal gas graph in the high-pressure zone. This deviation
from the graph of the ideal gas is known as positive deviation. For this region, Z > 1.

For a fixed amount of real gas, the compressibility factor depends upon the pressure and
temperature of the gas.

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 04

Graphs of some real gases

N2 H2
Z
O2 CH4 Z>1
CO2
Ideal gas
Z=1

Z<1

O P

Special Cases of Van der Waals Equation

Case 1: At low pressure

When the pressure is low, the volume is going to increase. Now, from the Van der Waals equation,
we get,
 an 2 
 P +  (V − nb ) =
nRT
 V2 
The volume term changes as follows:
V − nb
If V increases, since the value of nb is very small, it can be neglected .
For n = 1, the equation becomes,
 a 
⇒ P + 2  V =
RT
 V 
 a 
⇒ PV +  2 × V  = RT
V 
On dividing both sides by RT , we get the following:
PV a
⇒ + = 1
RT VRT
a
⇒Z+ = 1
VRT
a
⇒ Z =1 −
VRT
Therefore, at low pressure, Z < 1.
This can be observed in the graph of a real gas that when the pressure is low, the compressibility
is less than one (except hydrogen gas).

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 05

Case 2: At high pressure

From the Van der Waals equation,

 an 2 
 P + 2  (V − nb ) =
nRT
 V 
The pressure term changes as follows:
an 2
P+
V2
an 2
If P increases, can be neglected as it is very small.
V2
For n = 1, the equation becomes,
⇒ P (V − b ) =
RT
⇒ PV − Pb =
RT
On dividing both sides by RT , we get the following :
PV Pb
⇒ − =1
RT RT
Pb
⇒Z− =1
RT
Pb
⇒ Z =1 +
RT
Therefore, at high pressure, Z > 1.
This can be observed in the graph of a real gas that when the pressure is high, the compressibility
is greater than one.

Case 3: At low pressure and high temperature

From the Van der Waals equation, we get,

 an2 
 P +  (V − nb ) =
nRT
 V2 
At low pressure, the volume increases,
If V increases, the value of nb can be neglected as it is very small.
Also, due to high temperature, the attractive forces are zero.
an 2
Therefore, can be neglected.
V2
For n = 1, the equation becomes ,
⇒ PV =
RT
PV
⇒ = 1
RT
Therefore, at low pressure and high temperature, Z = 1.
At low pressure and high temperature, a real gas behaves as an ideal gas.

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 06

NEET
Various Speeds of a Gas Molecule

Most probable speed

The speed possessed by the maximum number of molecules is known as the most probable speed.
The formula for the most probable speed is as follows,

2P
vmp =
ρ
Also, PMmolar = ρ RT

PM
⇒ ρ = molar
RT
Substituting ρ in vmp equation, we get the following:

2RT
vmp =
Mmolar

Example:
Let us take a sample of gas containing 12 molecules. Let the speed of molecules in km s-1 be
(1, 2, 3, 3, 3, 3, 4, 4, 5, 5, 6, 6).

3 km s-1 (4 molecules)
4 km s-1 (2 molecules)
5 km s-1 (2 molecules)
6 km s-1 (2 molecules)
1 km s-1 (1 molecule)
2 km s-1 (1 molecule)

• Maximum speed = 6 km s-1

• To calculate most probable speed,
We can observe that 3 km s-1 is possessed by 4 molecules out of 12.
So, vmp = 3 km s-1

Average speed

The arithmetic mean of the speeds of the molecules in a gas at a given temperature is known as
the average speed of the molecules.
v1 + v2 + v3 +  + vn
v avg =
n
The formula for average speed is as follows:

8P
vavg =
πρ
Also, PM molar = ρ RT
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 07
v1 + v2 + v3 +  + vn
v avg =
n
The formula for average speed is as follows:

8P
vavg =
πρ
Also, PMmolar = ρ RT

PM
⇒ ρ = molar
RT
On substituting ρ in vavg equation,we get the following:

8RT
vavg =
π Mmolar

Root mean square speed

The square root of the mean square of the speed of all the molecules of a gas is known as the root
mean square speed of the gas.

v12 + v22 + v32 +  + vn2

vrms =
n
The formula for root mean square speed is as follows:

3RT 3RT 3 kT
vrms
= = =
Mmolar mN A m

We can observe that,

vrms ∝ T ⇒ With increase in T , vrms also increases.

1
vrms ∝ ⇒ With increase in m, vrms decreases.
m

• The root mean square speed of the gas molecules is in the order of km s-1.
• At T = 0 K (absolute zero temperature), vrms = 0
• A planet will have an atmosphere only if vrms < ve, where ve is the escape velocity.
• The Moon has no atmosphere because vrms of the gas molecule is more than the escape
velocity (ve).

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 08

Comparison between vrms, vavg and vmp

The ratio of all the speeds is as follows,

v mpv mp
: v:avgvavg vrms
: v:rms

2RT
2RT 8RT
8RT 3RT
3RT
⇒⇒ : : : :
Mmolar π M
Mmolar π molar
Mmolar Mmolar
Mmolar

88
⇒⇒2 :2 : : :3 3
ππ
v mpv mp
Therefore,
Therefore, < v<avgvavg vrms
< v<rms

Distribution Of Molecular Speeds

Maxwell plotted the graph between the fraction of

molecules and the speed of molecules. It is known as f (v)
Maxwell's speed distribution curve.
From the graph, we can observe the following:
• In the region of low speed, there are very few
molecules.
• In the region of high speed, there are very few
molecules.
• The peak of the bell curve represents the most
probable speed.
O v
• Since vavg > vmp, it lies in the right of the peak where vmp vavg vrms
the velocity increases. Low speed High speed
• Since vrms > vavg, it lies to the right of the average
speed.

Effect of temperature on velocity distribution

f (v)

The variation of the fraction of molecule vs speed T1 < T2

graph due to the temperature is as shown in the figure.
T1
From the graph, we can observe the following: T2
• When the temperature increases, the peak shifts
towards the right.
• The most probable speed increases with
temperature.
O
v

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 09

Free Path

The distance travelled by a gas molecule between two successive collisions is known as the free
path.
For a gas molecule having n number of collisions, there are n number of free paths:
λ 1, λ 2 , λ 3 , λ 4 , λ 5 ...... λ n

Mean free path

The average distance travelled by a gas molecule between two successive collisions is known as
the mean free path.
λ +λ λ+ +λ λ+ +λ λ+ +λ λ+ +λ ......
++ λ+
...... n λn
λ mean = =1 1 2 2 3 3 4 4 5 5
λ mean
n n
TheThe
mean freefree
mean path depends
path on on
depends twotwo
factors:
factors:
1 1
1. λ1.mean ∝ ∝
λ mean
Density of the
Density molecules
of the molecules
N N
Also, density
Also, of molecules
density = =
of molecules
V V
1 1
Therefore,
Therefore,λ mean ∝ ∝
λ mean
N N
V V
1 1
λ mean
2. 2. ∝ ∝
λ mean
Size of the
Size molecules
of the molecules
1 1
⇒ λ⇒mean ∝ ∝2 2
λ mean
d d

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 NOTE
P H Y S I C S

KINETIC THEORY
DEGREE OF FREEDOM

What you already know What you will learn

• Compressibility factor • Pressure of an ideal gas

• Special cases of Van der Waals • Relation between pressure and
equation translational kinetic energy
• Various speeds of gas molecules • Degree of freedom
• Maxwell’s speed distribution curve • Law of equipartition of energy
• Mean free path

NEET
Pressure of an Ideal Gas

Let's consider a cubical container filled with some

gas. Assume that there are N number of molecules
of gas and the mass of each molecule is m. We know y
that all the molecules of gases are moving randomly,
so their probability of moving in every direction is the vy v
same.
vz vx
As all the molecules of gases are the same, so from
these, let's take a molecule moving around the
container with velocity v. So, v can be resolved into x
three components along the x, y, and z-axis.

Instantaneous velocity, v = v x i + v y j + vz k
Since the probability of moving in every direction is L
z
the same,
So, vx = vy = vz

Time taken between two successive collisions

y
Let us assume that the molecule collides between two opposite walls of
the cubical container with side L along the x-axis.
The time between two successive collisions with wall A (∆t) is given as
follows: L
A
Distance travelled by the molecule between two successive collisions L
∆t =
Velocity of the molecule x
2L vx
⇒ ∆t =
vx L
z

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 02

Change in momentum

Let us assume the velocity along the positive x-axis as positive and the velocity along the negative
x-axis as negative. y
Momentum before the collision, pi = mvx
Momentum of the molecule after the collision, pf = -mvx
Therefore, change in the momentum is given as follows:
∆p = pf - pi
∆p = -mvx -mvx x
∆p = -2mvx
Magnitude of change in the momentum, |∆p| = 2mvx
z L

Force on a wall by a single molecule

∆p
Fx =
∆t
2mv x × v x  2L 
Fx =  Since ∆t 
2L  vx 
mv x2
Fx =
L

Total force on wall for N molecules

mv x21
Force due to first molecule, Fx1 =
L
mv 2x2
Force due to second molecule, Fx2 =
L
th
mv 2xN
Similarly, force due to N molecule, FxN =
L
Total force on the wall ( Fx , net ) = Fx1 + Fx2 +  + FxN
mv 2x1 mv x22 mv 2xN
⇒ Fx , net = + +  +
L LL
m 2
⇒ Fx , net=  v x + v x + v x +  + v 2x 
2 2

L  1 2 3 N 

Root mean square velocity along the x-axis is,

v 2x1 + v 2x2 + v x23 +  + v x2N
v x , rms =
N
v + v 2x2 + v 2x3 +  + v 2xN
2
x1
⇒ v 2x , rms = < v 2x > =
N
⇒ v 2x1 + v 2x2 + v 2x3 +  + v 2xN = N < v 2x >
Substituting it in the force equation, it changes as follows:
m 2
Fx , net
= v x + v 2x + v 2x +  + v 2x 
L  1 2 3 N 

mN
⇒ Fx , net = < v 2x >
L

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 03

We know that the probability of moving in every direction is the same,

< v 2x > = < v 2y > = < vz2 >
Now, the magnitude of the net velocity is as follows :
< v 2 > = < v 2x > + < v 2y > + < vz2 >
⇒ < v 2 > = 3 < v x2 >
< v2 >
⇒ < v 2x > =
3
Substituting this value in the force equation, we get the following:
mN 2
Fx , net= < vx >
L
mN 2
⇒ Fx , net= <v >
3L

Pressure on the surface due to gas molecule

mN
Fx , net= < v2 >
3L
Area of the surface, A = L2
Fnet
Pressure on the surface, P =
A
mN < v > 2
⇒P=
3 L × L2
mN < v 2 >
⇒P=
3V
< v 2 > =Mean square velocity of molecules
⇒ < v 2 >= vrms
= Root mean square velocity of molecules
1 mN 2
⇒P= vrms
3 V
We know , N × m = M = Net mass of gas
1M 2
⇒ P = vrms
3V
M
Also, =ρ
V
1 2
∴ P =ρ vrms
3

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 04

Relation Between Pressure and Translational Kinetic Energy

1
Kinetic energy, KE = Mvrms
2

2
1M 2
Also, P = vrms
3V
1
⇒ PV = Mvrms
2

3
For one mole of ideal gas, PV = RT ,
1
⇒ RT = Mvrms
2

3
⇒ 3 RT = Mvrms
2

Dividing both sides by 2,

3 RT Mvrms
2
⇒ =
2 2
3
⇒ KE =RT
2

Degree of Freedom ( f )

The number of possible independent motions of a system is known as the degree of freedom of
the system.

Degree of freedom

Translational Rotational Vibrational

NEET
General Expression for the Degree of Freedom

The general expression for the degree of freedom is given as follows:

f = 3A - B
Where,
A = Number of independent particles
B = Number of independent restrictions
For a monatomic gas
A = Number of independent particles = 1
B = Number of independent restrictions = 0

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 05

Therefore, degree of freedom is given as follows,

f = 3A - B
f = (3 × 1) - 0
f=3
For an optimum temperature, the gas atom will possess only translational motion. As the radius is
very small, we neglect the rotational motion. Also, due to less temperature, vibration motion can
also be neglected.
Therefore, f = 3 (Translational)
For a diatomic gas

A = Number of independent particles = 2

B = Number of independent restrictions = 1
Therefore, the degree of freedom is,
f = 3A - B
f = (3 × 2) - 1
f=5
A diatomic gas also has 3 translational motion along x, y, and z-axis.
Also, the molecule can rotate about y and z directions.
z y

z y
Therefore, f = 3 (Translational) + 2 (Rotational)
At high temperature,
f = 3 (Translational) + 2 (Rotational) + 2 (Vibrational)
For a triatomic gas (non-linear)

A = Number of independent particles = 3

B = Number of independent restrictions = 3
Therefore, the degree of freedom is,
f = 3A - B
f = (3 × 3) - 3
f=6

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 06

A triatomic gas has 3 translational motions along x, y, and z-axis and three rotational motions about
x, y, and z-axis.
Therefore, f = 3 (Translational) + 3 (Rotational)
y y

x x

x
z y z z

Law of Equipartition of Energy

The total energy of a gas is distributed uniformly along all the degrees of freedom. This is known
as the law of equipartition for energy.
1
Energy along the degree of freedom = KT
2
1. For monatomic gas
Degree of freedom, f = 3
1 3
Total energy for each molecule = KT × 3 =KT
2 2
2. For diatomic gas
Degree of freedom, f = 5
1 5
Total energy for each molecule = KT × 5 =KT
2 2
3. For a triatomic gas (non-linear)
Degree of freedom, f = 6
1 6
Total energy for each molecule = KT ×=
6 KT
= 3KT
2 2

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